Method of stress corrosion cracking mitigating for nuclear power plant structural materials

ABSTRACT

The object of this invention is to provide a method for mitigating a stress corrosion cracking of reactor structural material which makes it possible to suppress the rise in the main steam line dose rate without secondary effects such as a rise in the concentration of radioactive cobalt-60, etc. in the reactor water. Hydrogen and a reductive nitrogen compound containing nitrogen having a negative oxidation number (for example, hydrazine) are injected into the core water of boiling water nuclear power plant. By injecting the reductive nitrogen compound containing nitrogen having a negative oxidation number into the core water, the stress corrosion cracking of structural material of reactor can be mitigated without side reactions such as a rise in the concentration of cobalt-60, etc.

The present application is a Divisional Application of application Ser.No. 12/213,316, filed Jun. 18, 2008; which is a divisional ofapplication Ser. No. 10/896,092, filed Jul. 22, 2004 now abandoned, thecontents of which are incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to a technique for a preventive maintenance ofboiling water nuclear power plant (hereinafter, referred to as “BWR”),and particularly to a method for mitigating a stress corrosion cracking(hereinafter, referred to as “SCC”) of nuclear power plant structuralmaterials.

BACKGROUND OF THE INVENTION

In BWR, it is an important problem to suppress the SCC of the materialsconstructing the core structures and pressure boundaries (stainlesssteel, nickel-base alloys) from the viewpoint of improving the plantoperating rate. SCC takes place when the three factors (materials,stress, environment) fall on one another. Accordingly, SCC can bemitigated by mitigating at least one of the three factors.

When a plant is operated, the core cooling water is radioactivelydecomposed by the intense gamma and neutron rays emitted from the core.As its result, the structural materials constructing the in-corestructures and pressure boundaries come to be exposed to the corecooling water containing oxygen and hydrogen peroxide (both are theproducts of radiolysis) in an amount of several hundreds ppb and havinga high temperature (in this invention, a temperature of 100° C. or moreis referred to as high temperature; and the outlet temperature of coreis 288° C. at the time of normal power operation). FIG. 2 illustratesthe relation between crack growth rate (hereinafter, referred to as“CGR”) and electrochemical corrosion potential (hereinafter, referred toas “ECP”). It is apparent from FIG. 2 that CGR decreases when ECP drops.FIG. 3 illustrates the results of measurement on the relation betweenthe concentrations of oxygen and hydrogen peroxide and ECP of type 304stainless steel (hereinafter, referred to as “304SS”) inhigh-temperature water. Both oxygen and hydrogen peroxide show a higherECP at a higher concentration. Accordingly, for mitigating SCC ofstructural materials exposed to the cooling water of reactor, it isnecessary to reduce ECP, or to lower the concentrations of oxygen andhydrogen peroxide present in the reactor water.

As a technique for solving this problem, the technique of addinghydrogen from the feed water system (hereinafter, referred to as“hydrogen injection”) can be referred to. Hydrogen injection is atechnique of reacting the injected hydrogen with the oxygen and hydrogenperoxide formed by the radiolysis of water to return them to water, andthereby decreasing the concentrations of oxygen and hydrogen peroxide inthe reactor water. If the hydrogen injection is carried out, however,radioactive nitrogen 16 (hereinafter, referred to as “N-16”) formed bythe radio-activation of water becomes readily migrating together withsteam, and this N-16 enhances the dose rate of turbine building. FIG. 4illustrates the relation between the concentration of hydrogen in thefed water and effective oxygen concentration ((oxygenconcentration)+0.5×(hydrogen peroxide concentration)) and the relationbetween the concentration of hydrogen in the feed water and the relativevalue of main steam line dose rate. It is apparent from FIG. 4 that anincrease in hydrogen concentration in the feed water brings about a risein the relative value of main steam line dose rate, though it causes adecrease in the effective oxygen concentration.

For solving this problem, a technique of making an element of theplatinum group adhere to the surface of material and therebyaccelerating the reaction between hydrogen and oxygen and hydrogenperoxide (for example, see: (1) JP Patent No. 2766422). By thistechnique, ECP can be decreased while suppressing the rise in the mainsteam line dose rate.

SUMMARY OF THE INVENTION

If an element of the platinum group is made to adhere to the surface ofa material in order to accelerate the reaction between hydrogen andoxygen and hydrogen peroxide, however, there arises a new problem thatthe concentration of radioactive cobalt Co-60 in the cooling water forthe reactor rises.

It is an object of this invention to provide a method for mitigating thestress corrosion cracking of reactor structural materials by which therise in the main steam line dose rate can be suppressed without sidereactions such as the elevation of radioactive cobalt Co-60concentration in the cooling water of the reactor.

A reductive nitrogen compound containing nitrogen having a negativeoxidation number is injected into the reactor water of a boiling waternuclear power plant. By injecting a reductive nitrogen compoundcontaining nitrogen having a negative oxidation number into the reactorwater, the stress corrosion cracking of the structural material of thereactor can be mitigated without secondary effects such as the elevationof cobalt 60 (Co-60) concentration.

Other objects, features and advantages of the invention will becomeapparent from the following description of the embodiments of theinvention taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a drawing illustrating a BWR to which this invention isapplied.

FIG. 2 is a graph illustrating the relation between electrochemicalcorrosion potential and crack growth rate in 304SS.

FIG. 3 is a graph illustrating the relation between concentrations ofoxygen or hydrogen peroxide and electrochemical corrosion potential.

FIG. 4 is a graph illustrating the relations between hydrogenconcentration in the feed water and effective oxygen concentration,hydrogen concentration and relative value of main steam line dose rate.

FIG. 5 is a graph illustrating the relation between concentration ofadded hydrazine and electric chemical corrosion potential.

FIG. 6 is a graph illustrating the relations between concentration ofadded hydrazine and concentrations of oxygen, ammonia and hydrogen.

FIG. 7 is a graph illustrating the relation between concentration ofhydrogen in the feed water and effective oxygen concentration.

FIG. 8 is a graph showing the electrochemical corrosion potential of304SS in a case of adding methanol and carrying out γ ray irradiationand a case of adding methanol and carrying out no γ ray irradiation.

FIG. 9 is a drawing illustrating BWR to which this invention is applied.

FIG. 10 is a drawing illustrating the reductive nitrogen compoundinjecting apparatus.

FIG. 11 is a drawing illustrating the method for controlling the amountof injection of the reductive nitrogen compound in Example 2 of thisinvention.

FIG. 12 is a graph illustrating the relation between ammoniaconcentration and pH and electric conductivity.

FIG. 13 is a graph illustrating the relations between oxygenconcentration, hydrogen concentration, ammonia concentration and mainsteam line dose rate and the amount of injection of reductive nitrogencompound.

FIG. 14 is a drawing illustrating the method for controlling the amountof injection of reductive nitrogen compound and the amount of hydrogenin Example 3 of this invention.

FIG. 15 is a flow chart illustrating the control of the amount ofinjection of reductive nitrogen compound and the amount of injection ofhydrogen in Example 3 of this invention.

FIG. 16 is the first chart illustrating the method for controlling theamount of injection of reductive nitrogen compound, the amount ofinjection of alcohol and the amount of injection of hydrogen in Example4 of this invention.

FIG. 17 is the second chart illustrating the method for controlling theamount of injection of reductive nitrogen compound, the amount ofinjection of alcohol and the amount of injection of hydrogen in Example4 of this invention.

FIG. 18 is a graph illustrating the relations between concentration ofdissolved carbon dioxide and pH and electric conductivity.

EXPLANATION OF THE MARKS

-   -   3—Filter demineralizer for condensate;    -   5—Feed water heating system;    -   6—Feed water line;    -   8—Bottom drain line;    -   10—Reactor water clean up system line;    -   12—Reactor water filter demineralizer;    -   16—Primary loop re-circulation system line.

DETAILED DESCRIPTION OF THE INVENTION

Elevation of the main steam line dose rate is dependent on the hydrogenconcentration in the reactor water. The decreasing effect of theeffective oxygen concentration in the reactor pressure vessel bottomwater on the hydrogen concentration in the fed water is dependent on thedesigned conditions of the plant. As shown in FIG. 4, however, thehydrogen concentration in the fed water at which the main steam linedose rate begins to rise is not greatly dependent on the kind of plant,and stays at about 0.4 ppm. This is for the reason that most of theboiling water type reactors are so designed that the ratio of flow rateof feed water to flow rate in the core (average steam quality) comes toabout 13%, so that the amount of hydrogen injected into the reactorwater is not greatly different from one plant to another so far as theconcentration of the feed water is fixed. Accordingly, the chemicalreactions participated by N-16 in the core progress roughly under thesame conditions, and the change in the main steam line dose rate shows asimilar behavior. Accordingly, when a compound decreasing theconcentrations of oxygen and hydrogen peroxide in the reactor waterwithout greatly affecting the hydrogen concentration and giving thechanges of pH and electro conductivity falling in the standard ofcontrol is injected into the reactor water, ECP can be decreased and SCCcan be suppressed without causing a rise in the main steam system doesrate.

The present inventors have discovered that nitrogen compounds containinga nitrogen atom having an oxidation number smaller than that inmolecular nitrogen, such as hydroxylamine, carbohydrazide, hydrazine,ammonia, diazine and the like, (hereinafter, these nitrogen compoundsare referred to as “reductive nitrogen compounds”) are reductantssatisfying the above-mentioned conditions. As the first reason therefor,it can be mentioned that these compounds decrease ECP of the material byoxidation reduction reactions of the reductive nitrogen compoundsthemselves, even in the period in which dose rate of the irradiation issmall. FIG. 5 illustrates results of measurement of ECP of 304SS in thepresence of oxygen in water having a high temperature of 280° C.,wherein the injected reductive nitrogen compound is hydrazine. Asconcentration of hydrazine becomes higher, ECP decreases. If hydrazineconsumes oxygen and the decrease in oxygen concentration causes adecrease in ECP, ECP should decrease to −0.5 VvsSHE in the presence ofexcessive hydrazine. According to the result of actual (SHE), which isprobably attributable to an oxidation reduction reaction of hydrazine.Further, from the results of the measurement, it has become apparentthat ECP reaches a saturation when concentration of added hydrazineexceeds a definite value. This means that the time period of thehydrazine-oxygen reaction is in an order of second, in water of hightemperature. Accordingly, it can be expected that, even in the case ofBWR where it takes a time period of second order from entrance of thewater to its arrival at the core, the decrease will show a tendency ofsaturation. Thus, the inventors have confirmed that ECP can be decreasedby injecting a reductive nitrogen compound, and have found that ECP canbe decreased economically by placing an upper limit on the amount ofinjection.

As the second reason, it can be pointed out that a reductive nitrogencompound reduces oxygen and hydrogen peroxide according the (Equation 2)and (Equation 3), when the reductive nitrogen compound is oxidized toform a molecular nitrogen according to (Equation 1). In the time periodwhen the irradiation has a high dose rate, this reaction is acceleratedby formation of radials, etc.2N^(−n)−nR

N₂+2ne ⁻+R^(2n+)  (Equation 1)O₂+4H₂O+4e ⁻

4OH⁻  (Equation 2)H₂O₂+2e ⁻

2OH⁻  (Equation 3)(R designates the residual part of the moleculeof reductive organic compound.)

As the reductive organic compound, hydrazine is preferable. This is forthe following three reasons.

(1) Hydrazine reacts with oxygen and hydrogen peroxide as expressed by(Equation 4) and (Equation 5) to form nitrogen molecule and water whichdo not affect pH and conductivity. Accordingly, no release of hydrogentakes place. If the compound contains carbon, carbon dioxide is formed,which forms carbonic acid causing subsidiary effects of a rise inelectro conductivity and a decrease in pH. However, hydrazine containsno carbon, and therefore such a problem does not arise.N₂H₄+O₂

N₂+2H₂O  (Equation 4)N₂H₄+2H₂O₂

N₂+4H₂O  (Equation 5)(2) Hydrazine is higher than hydrogen in the reaction rate with oxygenand hydrogen peroxide. Accordingly, hydrazine rapidly reacts to formnitrogen and water, and the rise in electric conductivity, caused by itsresidence, is suppressed.(3) Hydrazine is a liquid substance and chemically stable, so that it iseasy to handle. It can be injected by means of a pump even into a siteof high pressure.

However, when subjected to γ ray irradiation, hydrazine undergoes thereaction of (Equation 6), and releases ammonia and hydrogen in additionto nitrogen.N₂H₄

NH₃+(½)N₂+(½)H₂  (Equation 6)

However, even in this case, due to the γ ray exposure, the reactionbetween N2H4 and radical forms a N2H3 radial which reacts with oxygenquite rapidly. The inventors have found that, so far as the amount ofhydrazine is not excessive to oxygen or hydrogen peroxide, thequantities of ammonia and hydrogen formed by the reaction of (Equation6) are only slight, and the influence on the water quality and mainsteam line dose rate can be minimized.

In order to confirm the above-mentioned reaction, the inventors addedhydrazine to oxygen-containing water having a high temperature of 280°C. and irradiated the system with Co-60, and followed the variations ofoxygen concentration and by-product concentration based on hydrazineconcentration. The results are shown in FIG. 6. When oxygen wasexcessive to the hydrazine concentration based on the stoichiometricquantities of the reaction of (Equation 4), the oxygen concentrationdecreased without formation of ammonia or hydrogen. On the other hand,when the concentration of hydrazine was excessive as compared withoxygen concentration, oxygen was consumed and at the same time ammoniaand hydrogen were formed. From the results mentioned above, it wasconfirmed that, when oxygen is present in the system, hydrazine does notundergo the reaction of (Formula 6) present in the system, hydrazinedoes not undergo the reaction of (Formula 6) even in exposure to γ ray,but the hydrazine reacts with oxygen to form nitrogen and water.

Further, it became apparent that an excessive amount of hydrazine isdecomposed into ammonia and hydrogen when exposed to γ ray. Based onthis fact, the inventors found that the ammonia concentration in thecooling water in the reactor pressure vessel bottom can be used as anindication for controlling the amount of injected hydrazine. This is forthe reason that existence of ammonia indicates that hydrazine is presentat least in an amount enough for consuming the oxygen and hydrogenperoxide. Since ammonia forms ammonium ion and hydroxide ion in theneighborhood of room temperature, its existence can be indirectlyconfirmed by measuring conductivity or pH. On the other hand, whenhydrazine is insufficient, ammonia is not formed. Accordingly, theammonia concentration in the bottom of reactor is useful as anindication for judging the de-oxidant effect of hydrazine in the coolingwater of reactor.

The effect of injection of hydrazine can be surely evaluated bymeasuring ECP by the measurement of oxygen concentration in the coolingwater at the bottom of reactor pressure vessel or by using an ECP sensorprovided on the drain line led from the bottom of reactor pressurevessel, and thereby combining the effect of hydrazine injection with amonitor.

The inventors have found that the concentration of oxygen and hydrogenperoxide in the reactor water can be decreased more economically andwith smaller subsidiary effects by combining the injection of reductivenitrogen compound and the injection of hydrogen and appropriatelycontrolling their concentrations. Although the concentration of oxygenand hydrogen peroxide in the reactor water can be reduced by merelyinjecting the reductive nitrogen compound, it can generally be said thatthe price per mole of reductive nitrogen compound is higher than that ofhydrogen. Further, in this technique, a reductive nitrogen compound isinjected at a high concentration, and therefore the excessive reductivenitrogen compound emits ammonia to make an adverse influence, unless theamount of reductive nitrogen compound is strictly controlled so as tobecome an optimum amount for consuming oxygen and hydrogen peroxide.Accordingly, it is most desirable to convert the residual parts ofoxygen and hydrogen peroxide which has not been consumed by hydrogeninjection into water with the reductive nitrogen compound, because thistechnique can minimize the necessary amount of reductive nitrogencompound and gives a room to the control.

FIG. 7 illustrates the results of analysis of effective oxygenconcentration in the upper part of reactor which has been subjected tohydrogen injection. It is apparent that, if hydrogen injection iscarried out, the concentrations of oxygen and hydrogen peroxide in theupper part of reactor are decreased. This is for the reason that thehydrogen present in the cooling water at the bottom of reactor pressurevessel suppresses the formation of oxygen and hydrogen peroxide causedby the radiolysis of water in the core. This effect is not readilyobtainable even if a reductive nitrogen compound is added. If theconcentrations of oxygen and hydrogen peroxide in the upper part ofreactor is lowered, the amount of reductive nitrogen compound necessaryfor consuming the oxygen and hydrogen peroxide in the reactor coolingwater can be decreased. As has been mentioned above, an increase in themain steam line dose rate takes place when the hydrogen concentration inthe feed water has exceeded about 0.4 ppm. Accordingly, when hydrogenconcentration in feed water is 0.4 ppm or below, no rise in the mainsteam line dose rate takes place, and even if a reductive nitrogencompound is added, the hydrogen concentration in the reactor coolingwater does not increase greatly, so that combination of hydrogeninjection and addition of reductive nitrogen compound does not lead toan increase in the main steam line dose rate. Further, when injection ofhydrogen and addition of reductive nitrogen compound are combined, therearises a merit that the nitrogen molecule formed from reductive nitrogencompound is not readily oxidized into compounds having a higheroxidation number such as nitrous acid, nitric acid, etc. When the amountof reductive nitrogen compound is smaller than that of oxygen orhydrogen peroxide, the unreacted oxygen and hydrogen peroxide and theformed nitrogen coexist in the down-stream of the site where thereductive nitrogen compound has reacted completely. In such a site,there is a possibility that the nitrogen is oxidized to form nitrousacid and nitric acid, in some cases. Nitrous acid and nitric acid arenot desirable, because they make a cause of a rise in electricconductivity and a decrease in pH. Although these oxidative anions donot cause a marked acceleration of SCC, so far as they are present inthe cooling water for reactor only in a small amount, there is a fearthat they can cause a decrease in pH and thereby a decrease in thestability of the oxides present on the line surface or fuels, and theycan exercise an influence on the radioactivity concentration of corewater. It is preferable, accordingly, to use hydrogen injection incombination and thereby maintain the cooling water for reactor in areductive atmosphere, even amount of hydrogen injection can be optimizedby monitoring the main steam line dose rate or by measuring the hydrogenconcentration in the cooling water at the bottom of reactor pressurevessel.

Further, the inventors have found that alcohols (CnH2n+1OH; wherein n isa natural number) are compounds capable of decreasing the concentrationsof oxygen and hydrogen peroxide in the reactor cooling water withoutgreatly affecting the hydrogen concentration. An alcohol reacts withoxygen or hydrogen peroxide according to (Equation 7) or (Equation 8) toyield carbon dioxide and water.C_(2n)H_(2n+1)OH+(3n/2)O₂

nCO₂+(n+1)H₂O  (Equation 7)C_(2n)H_(2n+1)OH+3nH₂O₂

nCO₂+(4n+1)H₂O  (Equation 8)

However, unlike the case of hydrazine, the reactions of Equations 7 and8 do not take place in the absence of γ ray irradiation. In order toconfirm this fact, an alcohol (methyl alcohol) was injected into waterof high temperature (280° C.) and ECP of 304SS was measured in the caseof carrying out γ ray irradiation and in the case of not carrying out γray irradiation. The results are shown in FIG. 8. It is apparent fromFIG. 3 that ECP of 304SS is about 0.1V (SHE) when the dissolved oxygenconcentration is 300 ppb, and ECP decreases as the dissolved oxygenconcentration decreases, and ECP reaches about −0.5V (SHE) whendissolved oxygen is 10 ppb or less. It is considered that, when γ rayirradiation is not carried out, oxygen remains without reacting withmethanol and therefore ECP has become about 0.1V (SHE), while when γ rayirradiation is carried out, oxygen reacts with methanol to decrease theoxygen concentration so that ECP has become about −0.25V (SHE). Based onthis result, it has been confirmed that methanol reacts with oxygen onlywhen 7 ray irradiation is carried out.

On the other hands when an alcohol reacts with oxygen and hydrogenperoxide, CO₂ is formed, which reacts with water according to (Equation9) to form carbonate ion.CO₂+H₂O

H₂CO₃

H⁺+HCO₃ ⁻

2H⁺+CO₃ ²⁻  (Equation 9)

Thus, alcohols are disadvantageous in that they make higher theconductivity of reactor water and lower the pH value thereof.Accordingly, it is considered appropriate to use alcohols in combinationwith a reductive nitrogen compound such as hydrazine. Reductive nitrogencompounds such as hydrazine are reactive with oxygen and hydrogenperoxide even in the absence of γ ray irradiation, while alcohols suchas methanol do not react with oxygen and hydrogen peroxide in theabsence of γ ray irradiation. Therefore, it is considered that reductivenitrogen compounds such as hydrazine are higher in reactivity thanalcohols such as methanol, and preferentially react with oxygen andhydrogen peroxide. Thus, by injecting a reductive nitrogen with oxygenand hydrogen peroxide. Thus, by injecting a reductive nitrogen compoundsuch as hydrazine in an amount somewhat smaller than the stoichiometricamount of the reaction with oxygen and hydrogen peroxide, and injectingthe alcohol such as methyl alcohol in an amount needed for reacting theresidual oxygen and hydrogen peroxide, the formation of ammonia which isa problem arising when a reductive nitrogen compound such as hydrazineis injected in itself alone can be suppressed. Further, there is a meritthat pH can be returned to the neutral side by carbonate ion, even ifthe ammonia forms ammonium ion and shifts pH to the alkaline side.

Additionally saying, it can be expected that, by adding an ion, an oxideor a hydroxide of manganese, zinc, molybdenum, tungsten or the like tothe reactor water, an oxidation reduction reaction between thesesubstances and reductive nitrogen compound takes place to accelerate thereactions of (Formula 4) and (Formula 5), and thereby the concentrationsof oxygen and hydrogen peroxide are decreased, and thereby ECP isreduced.

Next, BWR to which this invention is applied will be explained withreference to FIG. 1. In BWR, a condenser 13, a condensate filterdemineralizer 3, a feed water pump 4, a feed water heater 5 and areactor pressure vessel 1 charged with a nuclear fuel are connected bymeans of feed water line 6, and the reactor pressure vessel 1 andturbine 2 are connected by means of main steam line 14 to form a closedloop. Using water as the reactor coolant, water is converted to steam inthe reactor pressure vessel 1. A turbine is rotated by the use of thissteam, and thereby a generator (not shown in the figure) is rotated togenerate electricity. The steam is returned to water in the condenser13, made free from impurities in the condensate filter demineralizer 3,and returned to reactor pressure vessel 1 through feed water heater 5 bymeans of feed water pump 4. Apart from it, the lower part of reactorpressure vessel 1 and inlets of re-circulation pump 7 and jet pump 15are connected by means of Primary Loop re-circulation system line 16.Heat output is increased by increasing the flow rate of cooling waterflowing into the core by means of Primary Loop re-circulation pump 7.ABWR has no Primary Loop re-circulation system line 16, and the PrimaryLoop re-circulation pump 7, but has a structure of internal pump wherethe Primary Loop re-circulation pump 7 is provided in the pressurevessel 1. Hereinafter, an explanation will be made by referring to areactor having a Primary Loop re-circulation system line 16. In thisreactor, the upstream side of the Primary Loop re-circulation systemline 16 and the reactor water clean up system 9, reactor water clean upsystem heat exchanger 11, reactor water filter demineralizer 12 and feedwater system line 6 are connected by means of reactor water clean upsystem line 10, and the reactor water is passed to the reactor waterfilter demineralizer 12 by means of reactor water clean up system pump 9to remove impurities from the reactor water. Further, a bottom drainline 8 is provided to connect the bottom of reactor pressure vessel 1 tothe reactor water clean up system line 10. Further, in the upper part ofthe core of the reactor pressure vessel 1, there is provided anemergency core cooling system for injecting water into the rector corein order to cool the core at the time of emergency and a control roddrive hydraulic system for injecting cooling water to drive the controlrod for controlling the nuclear reaction of the fuel in the reactor areprovided (not shown in the figure). Further, water qualities in thesystem lines are monitored by means of water quality monitors 21 to 25,and the dose rate of the main steam line 14 is monitored by means of themain steam line dose rate measuring equipment 26. In the case of ABWR,there is provided a reactor water clean up system line 10 for drawingout a part of the reactor water from the upper part of reactor pressurevessel 1, cooling it by passing it through reactor water clean up systemheat exchanger 11, removing the impurities from the reactor water in thereactor water clean up equipment and returning it to the feed water line6.

In the above-mentioned BWR, the time at which a reductive nitrogencompound is injected in order to mitigate SCC is roughly classified intothe following two times, and the site of injection varies depending onthe time of injection.

(1) At the times of start up and shut down—The time period of start upoperation of the reactor, namely from the drawing out of the control rodto the is injection of cooling water from water feed system; and thetime period of shut down, namely from the time of stopping the injectionof feed water from the water feed system to the time of wholly insertingthe control rod.(2) At the time of operation—The time period of starting up the reactor,the time period of normal operation, and the time period of shut down;provided that the period of (1) is excepted.

The time periods of start up and shut down are period in which hydrogenand reductive nitrogen compound cannot be sent into the pressure vesselof the reactor, even if hydrogen and reductive nitrogen compound areinjected into the cooling water from the feed water system. Therefore,it is necessary to inject hydrogen and reductive nitrogen compound intothe cooling water flowing in at least one systems selected from thePrimary Loop re-circulation system, reactor water clean up system,emergency core cooling system and control rod drive hydraulic systemwhich can feed cooling water to reactor pressure vessel, for injectinghydrogen and reductive nitrogen compound into the reactor pressurevessel. At the time of start up and shut down, the radiation emittedfrom the core has a weak intensity, so that in the case of hydrogeninjection, the efficiency of removal of oxygen and hydrogen peroxide isconsidered to be low. Thus, injection of reductive nitrogen compoundreactive with oxygen and hydrogen peroxide even in the absence of theaction of irradiation is particularly effective. Since steam flows intothe condensation tank only when the steam flow rate is low and theturbine by-path valve is open, the influence of flying out of ammoniacan also be neglected. Further, since the allowable range of ammoniaconcentration in the core water is broader than at the time of normaloperation, the effect of injection of reductive nitrogen compound isvery great in this period.

On the other hand, at the time of normal operation, a reductive nitrogencompound is injected from at least one system selected from the waterfeed system, Primary Loop re-circulation system, reactor water clean upsystem, emergency core cooling system and control rod drive hydraulicsystem. Since the point of hydrogen injection is usually selected fromthe sucking-in side of the condensate pump having a low pressure, thereis no problem in the positioning of hydrogen injection point andreductive nitrogen compound injection point, so that hydrogen injectionand reductive nitrogen compound injection can be carried outsimultaneously.

The main place at which oxygen and hydrogen peroxide are formed byradiolysis of water is the core of the reactor. The emergency corecooling system and the control rod drive hydraulic system, capable ofdirectly feed cooling water to the core, can directly inject hydrogenand reductive nitrogen compound into the generation source of oxygen andhydrogen peroxide, and therefore they have a merit of capable ofdecreasing oxygen and hydrogen peroxide in the early stage. Further,water is usually stagnated on the inner surface of emergency corecooling system and the surface is exposed to intense irradiation, as aresult of which such areas are apt to generate SCC. Thus, if reductivenitrogen compound is passed constantly, SCC of the lines can beprevented and integrity of the system used at the time of emergency canbe secured.

In the case that a reductive nitrogen compound is injected from the feedwater system line 6, it is preferable to feed the water to a downstreampoint of the feed water heater 5. Carbon steel is used as a material ofthe feed water system line 6, and oxygen is injected into the coolingwater flowing therein in order to suppress corrosion of the pipe line.There is a possibility that the reaction with oxygen is catalyzed by thematerial surface, so that the reaction between oxygen and reductivenitrogen compound can be unnegligible at the position having a largesurface area per unit volume of fluid as in the feed water heater 5,which can lead to a drop in utilization rate of the reductive nitrogencompound. Further preferably, it is desirable to inject the reductivenitrogen compound from downstream of water quality monitor 21 for thecooling water of feed water system line 6. In the water quality monitor21, the impurities present in the cooling water taken into the reactorpressure vessel is monitored by checking electric conductivity. This isfor the reason that, if the reductive nitrogen compound is injected intoupstream thereof, the electric conductivity rises when the reductivenitrogen compound is dissociated into ions, and the presence of impuritybecomes impossible to monitor.

In the case where a reductive nitrogen compound is injected from thereactor water clean up system line 10, it is preferable to inject itfrom a down-stream point of the reactor cooling water filterdemineralizer 12. This is for the reason that, when the reductivenitrogen compound is ionized, the ions are caught at the reactor waterfilter demineralizer 12, and the utilization rate of reductive nitrogencompound in the reactor pressure vessel 1 becomes lower. Furtherpreferably, the reductive nitrogen compound is injected from thedown-stream point of water quality monitor 24 which is located atdownstream of the reactor water filter demineralizer 12. In the waterquality monitor 24, the impurities in the cooling water passing throughthe reactor water filter demineralizer 12 are monitored by electricconductivity. If it is injected from the upstream thereof, theionization of reductive nitrogen compound brings about a rise inelectric conductivity, which makes it impossible to monitor the presenceof impurities.

EXAMPLES

Hereunder, examples relating to injection of reductive nitrogen compoundinto cooling water, according to this invention, will be mentioned.

Example 1

As the first example of this invention, an example in which only areductive nitrogen compound is injected at the times of start up andshut down will be mentioned. At the times of start up and shut down,temperature is low and γ-ray exposure is small, so that thewater-forming reaction between reductive nitrogen compound and oxygenand hydrogen peroxide does not take place readily. FIG. 5 illustrateshydrazine concentration dependence of ECP of 304SS, wherein hydrazinewas added as a reductive nitrogen compound. If the ECP dependence of CGRshown in FIG. 2 is taken into consideration, it is necessary to addhydrazine in an amount of 50 ppb or more or further preferably in anamount of 100 ppb or more in order to reduce CGR to 1/10 of that in thecase of no hydrazine injection. On the other hand, addition of 300 ppbor more brings about no change in the ECP-lowering effect. From theelectric conductivity dependence of CGR shown in FIG. 2, it is apparentthat, even when ECP is the same, a higher electric conductivity gives agreater CGR. Accordingly, it is not desirable to add hydrazine in anexcessive amount in order to increase electric conductivity of coolingwater. Based on the above-mentioned facts, it can be said that it ispreferable to control the hydrazine concentration so as to come to 300ppb or less or to control reductive nitrogen compound concentration soas to come to 9.4×10-6 mol/liter or less; and it is further preferableto control hydrazine concentration to 50 ppb to 300 ppb, namely tocontrol the reductive nitrogen compound concentration so as to come tofrom 1.5×10-6 to 9.4×10-6 mol/liter.

FIG. 1 illustrates one example of the system chart in a case that areductive nitrogen compound solution stored in the reductive nitrogencompound solution tank 41 is injected into Primary Loop re-circulationsystem line 16 by means of reductive nitrogen compound solutioninjecting pump 42. In order to adjust the concentration of reductivenitrogen compound to a prescribed concentration, the reductive nitrogencompound of which amount is calculated by the following Equation 10 isinjected:(Amount of injected reductive nitrogen compound)=(Prescribedconcentration of reductive nitrogen compound)×(Amount of cooling waterin the pressure vessel of reactor)÷(concentration of reductive nitrogencompound in the reductive nitrogen compound solution tank)  (Equation10)

After once completing the injection, injection of the consumed amount ofreductive nitrogen compound is enough for adjusting the reductivenitrogen compound concentration to the prescribed value. Concentrationof the reductive nitrogen compound is determined by analyzing theconcentration of reductive nitrogen compound in the sample taken outfrom the cooling water of the bottom part of reactor pressure vessel 1through the water quality monitors 22 and 23. The amount to bere-injected is calculated from the following (Equation 11).(Amount of reductive nitrogen compound to be injected)={(Prescribedconcentration of reductive nitrogen compound)−(Analyzed value ofreductive nitrogen compound concentration)}×(Amount of cooling water inthe reactor pressure vessel)÷(Concentration of reductive nitrogencompound in the reductive nitrogen compound solution tank)  (Equation11)

By intermittently carrying out the above-mentioned procedures ofanalysis and re-injection, concentration of reductive nitrogen compoundcan be controlled so as to come to the prescribed value. It is alsopossible to carrying out a continuous monitoring by measuring theelectric conductivity of the cooling water in place of intermittentlyanalyzing the concentration of reductive nitrogen compound. This is forthe reason that electric conductivity can be converted to concentrationof reductive nitrogen compound by previously determining thecoefficients a and b in (Equation 12) experimentally.(Concentration of reductive nitrogen compound)={(Electricconductivity)−b}÷a  (Equation 12)

In FIG. 1 is shown an example in which a reductive nitrogen compoundinjecting equipment is connected to the Primary Loop re-circulationsystem line 16. However, it is also possible to similarly control theinjection of reductive nitrogen compound by connecting the reductivenitrogen compound injecting equipment to the reactor water clean upsystem line 10, as shown in FIG. 9. The other system lines are alsosimilar.

FIG. 10 illustrates one example of the reductive nitrogen compoundinjecting equipment preferably usable for the injection whilecontrolling the amount of reductive nitrogen compound. This equipment isprovided with a reductive nitrogen compound tank 51, in addition towhich at least one of water level indicator 52, flowmeter 55 andintegrated flowmeter 57 is provided. In addition to them, a reductivenitrogen compound solution injection pomp 54 for injecting a solution ofreductive nitrogen compound into the cooling water, and a valve 53 and acheck valve 56 for preventing erroneous injection of reductive nitrogencompound or back-flow of cooling water are equipped, and they areconnected together by means of pipe lines. The tanks and lines are madeof a steel material, the surfaces to be contacted with the reductivenitrogen compound are preferably coated with a resin material such aspoly-tetrafluoroethylene resin to prevent a direct contact between steelmaterial and reductive nitrogen compound. This is for the reason that adirect contact between steel material and reductive nitrogen compoundcan cause a decomposition of the reductive nitrogen compound. Further,there is a possibility that, if a reductive nitrogen compound comes intoa direct contact with air, the reductive nitrogen compound can bedecomposed. For preventing this decomposition, it is advisable to bubblethe reductive nitrogen compound present in the tank with argon gas or tocover the liquid surface with argon or the like.

Example 2

Next, as the second example of this invention, an example in which onlya reductive nitrogen compound is injected at the time of operation willbe mentioned. Since temperature is high and γ-ray exposure is greatestat the time of operation, the water-forming reaction between reductivenitrogen compound and oxygen and hydrogen peroxide is accelerated.Accordingly it is necessary to inject the reductive nitrogen compoundcontinuously.

In FIG. 6 are shown the changes of oxygen and by-products in a case ofadding hydrazine as a reductive nitrogen compound to high-temperaturewater containing dissolved oxygen and carrying out a γ ray irradiation.In case that the concentration of reductive nitrogen compound does notreach the amount needed for converting oxygen to water, a residual partof oxygen remains. In case that the concentration of reductive nitrogencompound is higher than the amount necessary for converting oxygen towater, oxygen is consumed and ammonia is formed. Based on these facts,the proper amount of injected reductive nitrogen compound can becontrolled by using the concentrations of oxygen and ammonia containedin the reactor pressure vessel bottom water as indications. One exampleof the controlling method will be explained blow with reference to FIG.11.

If the amount of injection is increased stepwise, the oxygenconcentration in the cooling water reactor pressure vessel bottomdecreases is at first so as to match the step. The target value ofoxygen concentration is 10 ppb, and further preferably 5 ppb. So far asthe oxygen concentration is lower than the target, ECP can be loweredsufficiently and CGR can be made small. If the amount of injection ofreductive nitrogen compound is stepwise increased, ammonia becomesdetectable in the cooling water of reactor pressure vessel bottom. Sinceammonia increases the load of reactor water filter demineralizer andleads to a rise in electric conductivity, a lower ammonia concentrationis desirable. FIG. 12 shows the relations between ammonia concentrationand pH at room temperature and electric conductivity. From the viewpointof water quality management criteria of BWR, it is required that pH atroom temperature is 5.6 to 8.6, and electric conductivity does notexceed 1 μS/cm. Accordingly, it is preferable that ammonia concentrationin the reactor water does not exceed 4.2×10-6 mol/liter.

The oxygen concentration can be analyzed by means of a dissolved oxygenmeter; while the ammonia concentration can be analyzed by means of ionmeter, calorimetric analysis or ion chromatography. It is also allowableto use electric conductivity or pH as an indication in place ofanalyzing ammonia concentration, because electric conductivity and pHcan be converted to ammonia concentration based on FIG. 12.

As above, the amount of injection of reductive nitrogen compound isstepwise increased, and the amount of injection of reductive nitrogencompound at which the ammonia concentration or the electric conductivityand pH comes to lower than the target value is previously determined.After that time of the operation, the designed amount of reductivenitrogen compound is injected.

Otherwise, the range of amount of injection is determined, and reductivenitrogen compound is injected in that concentration range. It is alsoallowable to alter the amount of injection manually in the light ofmeasured values of pH and ammonia, or to provide a control system intowhich measured values are fed back and thereby control the amount ofinjection.

In this example, the mount of reductive nitrogen compound which must beinjected has been determined by taking oxygen concentration as anindication. It is also possible to use ECP of the plant-constructingmaterial immersed in the cooling water as an indication. This is for thereason that, as shown in FIG. 3, oxygen concentration has a 1:1correlation with ECP, oxygen concentration can be determined from ECP.

Example 3

Next, as the third example of this invention, an example in whichhydrogen and a reductive nitrogen compound are injected into the coolingwater will be mentioned. In case that hydrogen is injected, the hydrogenconcentration in the cooling water at the bottom of reactor pressurevessel increases. If the hydrogen concentration exceeds a definitevalue, dose rate of the main steam line can increase. Accordingly, it isnecessary to control the amount of injected hydrogen together with thereductive nitrogen compound to obtain an optimum condition. Sincehydrogen is usually cheaper in price than reductive nitrogen compound,it is preferable to increase the amount of hydrogen and decrease theamount of reductive nitrogen compound.

FIG. 13 diagrammatically illustrates the changes of concentrations ofoxygen, hydrogen and ammonia in the cooling water at the bottom ofreactor pressure vessel, and the dose rate of main steam line, in thecase of changing the amount of injection of reductive nitrogen compoundwhile keeping the injection of hydrogen constant. In FIG. 13 issimultaneously shown a case of changing the amount of hydrogeninjection. The dose rate of main steam line is taken to increase whenthe hydrogen concentration in the cooling water at the bottom of reactorhas exceeded a definite value. In FIG. 13, a and d denote the amount ofinjection of reductive nitrogen compound at which dose rate of mainsteam line increases; while b and c are amount of injection of reductivenitrogen compound where oxygen concentration reaches the lowered target(b) by injection of reductive nitrogen compound. In the case of (2)where the injection of hydrogen is large, a small amount of reductivenitrogen compound is enough for reaching the lowered target of oxygenconcentration (b), but the dose rate of main steam line begins toincrease before reaching that amount of injection of reductive nitrogencompound (a). On the other hand, when the amount of injected hydrogen issmall (1), the injected amount of reductive nitrogen compound is largerthan that in the case of (2), but at such an amount the dose rate ofmain steam line does not rise (d). From the economical point of view, itis preferable to determine the maximum (1) as in the case of hydrogeninjection (1). By stepwise changing the injected amounts of hydrogen andreductive nitrogen compound and determining the relation of FIG. 13,proper ranges of the injected amounts of hydrogen and reductive nitrogencompound can be determined.

On the other hand, it is expected from the relation shown in FIG. 13that, if the amount of injection of hydrogen is decreased, the amount ofinjection of reductive nitrogen compound necessary for reducing theoxygen concentration will increase. By utilizing this fact, properranges of injection of hydrogen and reductive nitrogen compound can bedetermined more efficiently. This method will be explained below byreferring to FIGS. 14 and 15.

As shown in FIG. 14, a reductive nitrogen compound and hydrogen arestepwise injected, by taking the oxygen concentration and ammoniaconcentration in the coolant in the reactor pressure vessel bottom asindications. Concretely saying, according to the flow chart of FIG. 15,the amount of injected hydrogen and the amount of injected reductivenitrogen compound are varied. At first, injection of hydrogen is carriedout at the critical amount of hydrogen injection giving a dose rate, inthe main steam line, not exceeding the lower limit of target value.Subsequently, the concentration of reductive nitrogen compound isstepwise increased. When main steam line dose rate has exceeded in thisprocess, the amount of injected hydrogen is decreased by a definiteamount. The concentration of reductive nitrogen compound is increasedwhile aiming at that the oxygen concentration will reach a value notexceeding the lower limit of target. By this procedure, the amount ofinjection of the reductive nitrogen compound giving an oxygenconcentration not exceeding the target value can be determined. Further,in the same manner as in Example 2, the amount of injected reductivenitrogen compound is stepwise increased to determine the range of theamount of injected reductive nitrogen compound giving an ammoniaconcentration not exceeding the upper limit. By the procedure mentionedabove, an amount of injection of reductive nitrogen compound giving anoxygen concentration not exceeding the lower limit of target is taken asa minimum value, and the amount of injection just before the ammoniaconcentration exceeds the aimed upper limit is taken as the upper limit.

In the subsequent period of operation, hydrogen and reductive nitrogencompound concentrations are so controlled as to come to the valuesdetermined above. It is also allowable to control the hydrogen injectionby using the hydrogen concentration in the reactor pressure vesselbottom as an indication, in place of main steam line dose rate. In thiscase, injection of hydrogen only is previously carried out, and therelations of main steam line dose rate and hydrogen concentration in thebottom of reactor pressure vessel to the amount of hydrogen injectionare determined, and further the relation between main steam line doserate and hydrogen concentration in the bottom of reactor pressure vesselis determined. Hydrogen concentration can be continuously monitored bythe use of dissolved hydrogen concentration meter. Further, it is alsopossible to use ECP of the plant-structural material dipped in coolingwater as an indication, as has been mentioned in Example 2.

Example 4

Next, as the fourth example of this invention, a method of injectinghydrogen, a reductive nitrogen compound and an alcohol into coolingwater will be mentioned. When hydrogen is injected, there is apossibility that the hydrogen concentration in the reactor pressurevessel bottom water increases, and if it exceed a definite value, mainsteam line dose rate increases, in the same manner as in Example 3. Whenan alcohol is injected, there is a possibility that, due to thecarbonate ion, pH becomes low or electric conductivity becomes high.Accordingly, it is necessary to control the amounts of injection ofalcohol and hydrogen together with reductive nitrogen compound, andoptimize the condition.

After determining the amount of injection of reductive nitrogen compoundand hydrogen according to the method mentioned in Example 3, alcohol isinjected so as to replace the reductive nitrogen compound and alcohol.Its amount is calculated according to the following equation 13:(Concentration of injected alcohol)=(Molar number of alcohol necessaryfor reacting with 1 mol of hydrogen peroxide)/(Molar number of reductivenitrogen compound necessary for reacting with 1 mol of hydrogenperoxide)×(Concentration of injected reductive nitrogen compound to besubtracted)  (Equation 13)

Concretely saying, it is advisable to replace the reductive nitrogencompound and alcohol stepwise while confirming that the change ofelectric conductivity of cooling water becomes smaller than the targetvalue, as shown in FIG. 16.

Otherwise, it is also allowable to determine the amount of alcoholinjection giving an electric conductivity smaller than the target valueand thereafter to inject the reductive nitrogen compound stepwise, asshown in FIG. 17. The concentration of dissolved CO2 formed from thealcohol can be calculated according to (Equation 7) and (Equation 8).From the relation between dissolved CO₂ concentration and pH at roomtemperature and electric conductivity shown in FIG. 18, theconcentration of dissolved CO₂ giving an electric conductivity smallerthan the target value can be read out. Accordingly, the alcoholconcentration giving an electric conductivity not exceeding the targetcan be determined. However, since there is a possibility that thereductive nitrogen can be consumed prior to the alcohol, it is advisableto confirm the effect by taking the oxygen concentration in the coolingwater and ECP of plant-structural material dipped in the cooling wateras an indication.

It should be further understood by those skilled in the art thatalthough the foregoing description has been made on embodiments of theinvention, the invention is not limited thereto and various changes andmodifications may be made without departing from the spirit of theinvention and the scope of the appended claims.

EFFECT OF THE INVENTION

According to this invention, a stress corrosion cracking of nuclearpower plant structural material can be mitigated without secondaryeffects such as rise in the cobalt-60 concentration and the like, byinjecting a reductive nitrogen compound containing a nitrogen having anegative oxidation number into a reactor water.

1. A method for mitigating a stress corrosion cracking of structuralmaterial in a nuclear power plant, comprising the step of: injectinghydrogen and a reductive nitrogen compound containing nitrogen having anegative oxidation number into a reactor water of a boiling waternuclear power plant, wherein said reductive nitrogen compound isinjected into the cooling water at the time of normal operation of thereactor, from at least one system line selected from the groupconsisting of a feed water system, a reactor water clean up system, aprimary loop re-circulation system, an emergency core cooling system anda control rod drive hydraulic system, wherein the injection of saidreductive nitrogen compound is controlled to set the concentration ofsaid reductive nitrogen compound in the cooling water at 9.4×10⁻⁶mol/liter or less, wherein said reductive nitrogen compound is injectedinto the cooling water at the time of normal operation of the reactor,from a system line of a reactor water clean up system, wherein saidreductive nitrogen compound is hydrazine, and wherein a site of theinjection of the reductive nitrogen compound from said reactor waterclean up system line is an injection connection provided on the lineconnecting the down stream of filter demineralizer and the reactorpressure vessel.